Pobation of new yobk



Patented Jan. 17, 1928.

UNITED! STATES PATENT OFFICE.

BALI B. TBUBLEB O E DORMONT, PITTSBURGH, PENNSYLVANIA, ASSIGNOR TO THE BOESSLEB 0: HASSLACHEB CHEMICAL COMPANY, OF NEW YORK, N. Y., A COB- POBATION OF NEW YORK.

IBTHOD OI MANUFACTURE OI. AC YL AMINES.

Io Drawing.

This invention relates to the preparation of acyl derivatives of primary and secondar amines. v

11 general, acyl derivatives of primary and secondary amines are made by causing an amine to react with one of the following compounds.-

(1) An organic acid in the presence of a dehydrating agent.

2 An anhydride of an organic acid.

3 A salt of an or anic acid in the presence of a mineral acid.

(4) An acyl chloride of an organic acid.

Anamlna.

Wherein R R and, R represent alkyl, anyl or cyclic groups or radicals and where R and R may also represent hydrogen. I have found that the amine 1nvolved in this reaction must be less basic than the ammonia that occurs in the byproduct of ammonium acid sulfate otherwise this reaction will not take place. I have also found that hydroxy amides, where the hydroxyl group is attached to the same carbon atom as the amide, group as in lactamide acid sulfate undergo other changes and do not satisfactorily react as do the other amide acid sulfates described in the examples given.

I have also foundthat this method of manufacture of ac l amines will in general allow the production of acyl amines which can be produced by the usual means of reacting an amine with an acid anhydride, but will not allow the production of ac 1 amines which cannot-be obtained from t e anh dride 'of an organic acid and an ami e. For exam 1e, acetanilid can be obtained either by heating aniline with acetic anh dride or with acetamide acid sulfate, but th e compound para acetyl amino phenol is not technically obtained by reacting p-ami- An amide acid lultate.

Appllcatlon filed December 27, 1926. 7 Serial No. 157,419.

I have discovered a new method for making acyl amines from primary and secondary amines, wherein many of the disadvantages common to the ordinary methods are done away with, and whereby an easily controlled reaction is obtained. 1 have found that when certain primary or secondary amines are caused to react with an amide acid sulfate that a combination between the two compounds results in the formation of acyl amines and simultaneously of ammonium acid sulfate as a by roduct.

This reaction is illustrate by the equation:

nohenol with either acetic anhydride or wit acetamide acid sulfate.

In order to illustrate my invention the following examples are given:

Example I.

F0rmgn2IZid.-One gram mol of formamide acid sulfate wei hin about 143.1 grams and one mol o aniline weighing about 93.1 grams were mixed and then heated with stirring up to 85 C. for about three hours. The reaction mixture gradually separated into two la ers the upper one being mainly formanihd and the lower one bemg mainly ammonium acid sulfate. The reaction mixture was allowed to cool to about and to it was added 100 rams of carbon tetrachloride which disso ved the formanilid. The carbon tetrachloride solution was then decanted and evaporated at reduced pressure, and there resulted an oily liquid that crystallized on standing. The crystalline compound was separated from the residual oily liquids by centrifu ing. The purified substance was found to ave a melting point of 47 to 48 C.

Upon analysis the compound was found to contain :-nitrogen, 11.56%; hydrogen,

5.57%; carbon, 69.35%; oxygen, 13.52% by difference.

When 121.1 grams of the compound was hydrolyzed by a solution of sodium hydroxide, 93 grams of aniline was recovered, while the water contained one mol (63 grams) of sodium formate in solution. The 11 drolysis so effected also establishes the identity of the compound.

The reaction between formamide acid sulfate and aniline, by which formanilid is produced, is illustrated by the equation:

Formamide acid suliate. Aniline.

Example II.

Aoet-toZuz'd.-One mol of acetamide acid sulfate weighing about 157.1 grams and one mol of p-toluidine weighing about 107 .1,

ams, were mixed in the presence of cart m tetrachloride and then heated to about 75 for three hours. The reaction mixture now consisted of a lower layer of ammonium acid sulfate and an upper layer of carbon tetrachloride in ,which the organic product of the reaction was dissolved. The carbon tetrachloride solution was separated, distilled from a water bath and finally under vacuum. The residue, which may be either solid or liquid depending upon purity, consisted essentially of acet-p-toluide. The pure compound was obtained by recrystallization from alcohol. Analyses showed that 149 grams of the compound contained 107 grams of p-toluidine and 43 grams of the acetyl radical obtained as grams acetic acid.

The melting point of the acet-p-toluide was found to be 109.0 to 109.3.

Example III.

' oughly cooled, then pulverized and stirred into 200 c. c. of cold water to leach out the ammonium acid sulfate byproduct; After standing four hours it was filtered off and stirred into 100 c. c. of water containing a little ammonia, then again filtered. The filter cake, when dry, consisted of forty-six grams of benzanilid of good quality. The melting oint of the crude material was 156- 157, an after being crystallized from alcohol it melted at 159.5 to 160.5 C. The yield was 93.5% 'of theory.

' E'hwmple IV.

Meta-d4 ormyl phenylene diamine-fine hundred fi y grams of formamide acid sulfate contained in a one liter flask was covrormmmd.

ered with 250 c. c. of carbon tetrachloride and to it was added 54 grams of metal phenylenediamine. The flask was provided with a reflux condenser and then heated about two hours at 7 576. The carbon tetrachloridewas then distilled off b placing the flask in a hot water bath. T e flask was then cooled and to it was added just enough ammoniacal alcohol to convert the b roduct of ammonium acid sulfate into (N 0,80 The product was washed with alcohol to remove unused m-phenylene diamine and then with water to remove the sulfate salts. The product obtained by this reaction was practically insoluble in water and alcohol. It was pinkish white in color and melted with decomposition about 300. The character of this compound agrees with the description of meta di formyl phenylene diamine as given in the literature. Analysis showed that this compound consisted of carbon, 59.00%; nitrogen, 8.43% to 8.4%; hydrogen, 4.84% to 4.7%; which agrees with meta di formyl phenylene diamlne in composition.

I claim:

1. Method of manufacture of acyl amines from those amines which contain at least one hydro en atom linked directly to nitrogen, which are less basic than ammonia and which react with acid anhydrides to form acyla-mines com risin reacting these amin'e's with amide aci sulp ates.

2. Method of manufacture of acyl amines from those amines which are less basic than ammonia and which react with acid anhy-,

drides to form acylamines comprisin reacting these amines with amide acid su phates.

3. Method of manufacture of acylamines from those amines which contain at least one hydrogen atom linked directly to nitro en, which are less basic than ammonia and w ich react with acid anhydrides to form acylamines comprising reacting these amines with formamide acid sulphate.

4. Method of manufacture of acyl amines from those amines which are less basic than ammonia and which react with acid anhydrides to form acylamines comprising reactllilg t:ahese amines with formamide acid sulp a 5. Method of manufacture of the acyl amines of the phenylene diamines comprising reacting them with amide acid sulphates.

6. Method of manufacture of the di form 1 phenylene diamines comprising reacting t e Ill corresponding phenylene diamines with formyl phenylenediamine comprising reactformamide acid sulphate. ing meta phenylene diamine with formamide 7. Method of manufacture of the acyl am acld sulphate. l0 ines of meta phenylenediamine comprising Signed at Pittsburgh in the county of 5 reactin meta'phenylene diamine with amide Allegheny and State of Pennsylvania this acid su phates. 20th day of December, A. D. 1926.

-8. Method of manufacture of meta di RALF B. TRUSLER. 

